KR101787153B1 - Gas sensor and method for producing the same - Google Patents
Gas sensor and method for producing the same Download PDFInfo
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- KR101787153B1 KR101787153B1 KR1020137000869A KR20137000869A KR101787153B1 KR 101787153 B1 KR101787153 B1 KR 101787153B1 KR 1020137000869 A KR1020137000869 A KR 1020137000869A KR 20137000869 A KR20137000869 A KR 20137000869A KR 101787153 B1 KR101787153 B1 KR 101787153B1
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
- G01N33/0004—Gaseous mixtures, e.g. polluted air
- G01N33/0009—General constructional details of gas analysers, e.g. portable test equipment
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/02—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
- G01N27/04—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance
- G01N27/12—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance of a solid body in dependence upon absorption of a fluid; of a solid body in dependence upon reaction with a fluid, for detecting components in the fluid
- G01N27/125—Composition of the body, e.g. the composition of its sensitive layer
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/02—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
- G01N27/04—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance
- G01N27/12—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance of a solid body in dependence upon absorption of a fluid; of a solid body in dependence upon reaction with a fluid, for detecting components in the fluid
- G01N27/125—Composition of the body, e.g. the composition of its sensitive layer
- G01N27/127—Composition of the body, e.g. the composition of its sensitive layer comprising nanoparticles
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
- G01N33/0004—Gaseous mixtures, e.g. polluted air
- G01N33/0009—General constructional details of gas analysers, e.g. portable test equipment
- G01N33/0027—General constructional details of gas analysers, e.g. portable test equipment concerning the detector
- G01N33/0036—Specially adapted to detect a particular component
- G01N33/0047—Specially adapted to detect a particular component for organic compounds
Abstract
The present invention relates to a gas sensor for detecting gases in air, in particular formaldehyde. The sensor preferably comprises at least one gas-sensitive region containing a layer on the substrate and a ternary compound In 4 Sn 3 O 12 as a gas-sensitive substance. In order to prepare the gas-sensitive region, flame spray pyrolysis (FSP) is carried out and organometallic compounds of indium and tin are used as reactants. The gas sensor is particularly suitable for on-line gas detection.
Description
The present invention relates to a gas sensor for detecting gases in air, in particular formaldehyde, and a method for manufacturing the sensor.
Formaldehyde is a chemical compound used industrially in a variety of ways. Formaldehyde is used in the manufacture of plastics, in the processing of wood as an adhesive in plywood boards and chipboards, as an insulation in the building industry, in the textile industry for spindle processing and easy-care processing And as a preservative in the agriculture and food industries. Formaldehyde is used as a disinfectant and is contained in paints, varnishes and carpets in some cases, as well as cosmetics, body and oral care products (1).
Furthermore, formaldehyde arises from the incomplete combustion process. For example, this process is found in the combustion engine of an automobile, in a foundry, in the production of plastic products, or in incineration of wood in a small combustion plant. In the same way, formaldehyde also occurs during smoking and causes air pollution (1).
Formaldehyde is a gaseous substance that can cause health problems such as eye irritation or mucous membrane irritation. Short term exposure causes eye and respiratory irritation at low concentrations: stimulates the eye from 0.01 ppm, stimulates the eyes and nose from 0.08 ppm, and stimulates the throat from 0.5 ppm. Condensed vapors above 10 ppm may cause severe irritation of the mucous membranes, including tears, coughing, and burning sensations in the nose and throat. Concentrations above 30 ppm lead to toxic edema and pneumonia in life-threatening lungs (1).
The chronic effects of formaldehyde are problems such as insomnia, lethargy, loss of motivation, loss of appetite or nervousness, eye irritation and conjunctivitis, skin irritation, chronic cough, cold and bronchitis, headache and depression. Furthermore, formaldehyde has also been suspected to be able to induce hypersensitivity, to cause cancer for some time, or to act as mutagenic or teratogenic in humans. For this reason, the German Health Authority introduced a Maximum Allowable Concentration (MAC) of 0.3 ppm (0.375 mg / m 3 ), which is even 0.1 ppm (0.125 mg / m 3 3 ) because in this case sustained exposure is expected (2).
For this reason, effective and rapid detection and measurement of formaldehyde in air has great importance.
Several methods for detecting formaldehyde in air are known from the prior art (a summary of known methods is provided, for example, in the publications of H. Nishikawa and T. Sakai (3)).
For example, gas chromatography (GC) analysis and high performance liquid chromatography (HPLC) analysis are analytical standard methods. To assess workplace hazards, the National Institute for Occupational Safety and Health (NIOSH) standardized several analytical methods for detecting formaldehyde in the air.
In the case of NIOSH Method 2016, for example, the test air passes through a medium made of silica gel coated with dinitrophenylhydrazine (DNPH). Hydrazine can be identified and quantified as a stable derivative using HPLC, GC / FID, GC / ECD or diode array detectors (4).
NIOSH method 2541 is based on GC / FID-analysis. Here, the test air passes through a tube coated with 2-hydroxymethylpiperidine (2-HMP). The formaldehyde of the sample reacts with 2-HMP to produce the oxazolidine derivative which is subsequently desorbed and analyzed by gas chromatography (5).
The NIOSH method 3500 is based on spectroscopic measurements. In the presence of sulfuric acid, the condensation of two molecules of chromophilic acid and formaldehyde takes place and a red carbenium cation is formed. After that, spectroscopic verification is carried out by measurement at 580 nm (6).
A substantial disadvantage of these analytical methods is the need to precisely prepare an air sample for the derivatization of formaldehyde, and the actual measurement must be carried out in a special laboratory. Online detection is not possible using these methods.
In addition to the analytical methods, a number of instrumental methods are known in the art. Formaldehyde can be detected using a photoionization detector after ionization with an argon lamp due to its 10.87 eV ionization potential. A major drawback of the method is that it also involves a tremendous effort.
Another method for formaldehyde detection is based on electrochemical cells. This method has the disadvantage that the equipment required for the measurement is very expensive. In addition, periodic recalibration of the measuring equipment is required, and battery life is limited to less than one year.
In addition, fluorescence-based methods for detecting formaldehyde, for example detection methods based on Hanzsch reactions, are known in the art. In practice, the method provides relatively high selectivity, but the corresponding measuring device is very expensive. Another disadvantage is the precise manufacture of air samples in which formaldehyde is correspondingly derivatized for measurement (7).
The above-described methods for detecting formaldehyde require much effort for the analysis of the equipment for derivatization and the subsequent formaldehyde, so these methods can only be used in large laboratories and the results are only available after long manufacturing times.
MOX-based methods for enabling on-line measurement of formaldehyde concentrations are also known in the art. In this case, the formaldehyde from the sample reacts with the metal oxide sensor, whose conductivity is changed by the reaction. Sensitive layers of oxides of different combinations of Zn, Ni, Sn, Cd, In and other metals are used as sensors. Table 1 provides an overview of the metal oxides known to date, used for the detection of formaldehyde, along with their measurement ranges and the author's description.
Table 1 shows that all gas sensors known to date and whose function is based on metal oxides (except for ZnO nanowires) act at very high concentration levels well above the maximum allowable value of the law, or have low sensor signals (A sensor signal covering a concentration range of 1000 times and in the range of only 1 to 1.6 does not allow the determination of the relevant concentration grading). Regarding nanowires, problems with long-term stability of sensors have been reported in Chu's publication (23).
US 2002/0118027 A1 discloses a nano-structured anodic aluminum oxide substrate for a gas sensor having a gap parallel to the electrode. The sensitive material may be deposited in the pores to significantly raise the surface of the sensitive layer relative to the flat applied layer and thus increase the sensitivity of the sensor. The materials used for the sensitive layer play a less important role in the literature. The cost for manufacturing such a substrate can be relatively high.
It is therefore an object of the present invention to provide a novel gas sensor which can be manufactured at a competitive cost with a high sensitivity that enables on-line detection.
According to
The material In 4 Sn 3 O 12 is well known from the prior art for use in the production of radiation emission and electrochromic devices (DE 10 2007 049 005 A1, DE 10 2004 001 508 T2, DE 00 0060 017 440 T2) . Such materials have not yet been described in connection with the manufacture of sensors.
In the scope of the present invention, it has been unexpectedly found that the material In 4 Sn 3 O 12 possesses the characteristics of an effective gas sensor.
In the sensor according to the invention, it is crucial that the material In 4 Sn 3 O 12 is present as a ternary oxide (mixed oxide phase) and not a simple metal oxide mixture. The material is an independent material and more importantly an important phase having its own structure. For example, the material is described in (29) and analyzed in detail. No mention or implication can be found from the prior art for using In 4 Sn 3 O 12 on the mixed oxide phase as a sensitive layer in a gas sensor.
The sensor according to the invention comprises at least one gas-sensitive region of In 4 Sn 3 O 12 , said region preferably being in the form of a layer. In the case of gas detection using a sensor according to the invention, its sensitive layer is contacted with a gas sample (e.g. air). After the reaction, the electrical properties of the sensitive layer change, which can be measured as a change in electrical impedance, a change in workfunction and / or capacitance. It is desirable to measure the change in resistance.
According to a preferred embodiment of the invention, the sensor according to the invention is used for detecting formaldehyde. By using the sensor according to the invention, sensor signals in the range of 2.1 to 10.9 can be obtained for formaldehyde in the concentration range of 20 ppb to 180 ppb. Compared to a commercially available reference sensor, the sensor according to the invention exhibits an increase of up to 640% in the sensor signal. This corresponds to a
In a further embodiment of the present invention, the sensor is used to detect gases such as NO 2 , alcohol, CO, and the like.
A method for manufacturing a sensor according to the present invention is also a subject of the present invention. For this purpose, gas-sensitive In 4 Sn 3 O 12 Layer is applied on the substrate using the so-called FSP-method (flame spray pyrolysis).
The FSP-method is well known from the prior art for providing Pd / SnO 2 sensors (L. Maedler et al., 28). Compared to the FSP-method, the original step of the method is to identify suitable raw materials for the production of the In 4 Sn 3 O 12 layer. It has been found that particularly good results can be achieved in the production of the sensitive layer when using the organometallic compounds of indium or tin dissolved in an organic solvent as raw material in the scope of the present invention. In particular, indium acetyl acetone and tin-2-ethylhexanoate dissolved in xylene are suitable for preparing the In 4 Sn 3 O 12 layer.
Furthermore, it has been found that the concentration of the raw material plays an important role in the method for producing the gas-sensitive layer for the sensor according to the invention. The best results were achieved when the raw materials indium acetylacetone and tin-2-ethylhexanoate were used in each case at concentrations of 0.05 to 0.7 moles (moles per liter of solvent).
Another subject of the present invention is the use of a gas sensor as described above for detecting gas in a residential environment to enable on-line analysis of corresponding air contamination. In addition, the sensor is adapted to enable air analysis in industrial facilities where formaldehyde is handled and thus exposure to humans and the environment can not be ruled out.
The sensor according to the present invention is a new serious event in the prior art, because until now it has not been possible to detect formaldehyde by on-line application.
Additional advantages, features and applicability of the sensor and the method for manufacturing the same are substantially described using the embodiments described below with reference to the drawings.
1 shows sensor signals of the sensor according to the present invention according to tin concentration. 0% corresponds to pure In 2 O 3 , and 100% corresponds to pure SnO 2 . The maximum sensor signal is obtained at a Sn ratio of 43%, which corresponds to the pure phase In 4 Sn 3 O 12 . The rectangle represents the sensor signal at a formaldehyde concentration of 180 ppb, and the dot represents the sensor signal at a concentration of 100 ppb.
Figure 2 shows the curve of the resistance as a function of time for the measurement of different formaldehyde concentrations with the sensor according to the invention compared to the measurement of known prior art instruments. The solid line corresponds to a pure In 4 Sn 3 O 12 having a phase corresponding to the measurement of the sensor according to the present invention, and the dashed line corresponds to the Appliedsensor MLC (2.3 V), and a broken line (dashed line) is a Figaro TGS 2620 (5.0 V) sensor do. It is immediately possible to see a visual comparison that the sensor signal for the sensor according to the present invention is significantly larger than that of the known sensor of the prior art due to the logarithmic plotting. The concentrations associated with the individual signal steps are 20, 40, 80, 100, 120, 160 and 180 ppb, and then the order is repeated.
Figure 3 : Curve of the sensor signal as a function of time at different formaldehyde concentrations in humid air (50% relative humidity). The sensor signal of the improved In 4 Sn 3 O 12 phase (circle) can be clearly observed in every concentration area compared with the sensor signal measured with the reference sensor of Figaro (square) and Applied sensor (triangle) known in the prior art. Both of these reference sensors, widely known in the prior art, work on the basis of changes in resistance, similar to sensors according to the present invention, but their sensitive layers are based on tin dioxide.
Figure 4 : Sensitivity of the sensor according to the invention compared to two reference sensors known in the prior art. The squares correspond to the Figaro TGS 2620, the triangles correspond to the Applied Sensors MLC and the dots or stars indicate the sensitivity of the In 4 Sn 3 O 12 sensor according to the invention on different days. According to the definition of sensitivity, here a change in resistance compared to a change in analyte concentration is shown for the analyte concentration. It is clearly identifiable that the sensor according to the invention has a sensitivity which is 100 times higher than that of a known reference sensor of the prior art.
Example
Fabrication of materials and deposition on sensor substrates
Phase diagrams of a solid solution of SnO 2 in In 2 O 3 (I. Isomaeki et al. (29)) show that phase In 4 Sn 3 O 12 is formed in the temperature range of about 1600 to 1900 K The metastable high temperature standing is obvious. When the temperature is slowly lowered (vertically down in the state diagram), the phase is decomposed into a solid solution of ITO (indium tin oxide) and SnO 2 . In the case of a composition having a Sn content exceeding 10%, In 4 Sn 3 O 12 can always be obtained by selection of an appropriate temperature. If the temperature rises more, finally an ionic fluid is formed. The method of synthesis of the flame spray pyrolysis method thus makes it possible to prepare the phase in the flame and onto the cooled substrate, ensuring that the phase is quenched and thus maintained.
Tin-doped (doped) In 2 O 3 ( ITO) to prepare a metal oxide, an organometallic compound, for example acetylacetone indium (99.9% pure, Strem) and tin 2-ethylhexanoate (99.5% pure, Strem ) Was used in flame spray pyrolysis (FSP). The organometallic compound, hereinafter referred to as a precursor, was dissolved in an organic solvent (for example toluene (99.95% pure, Strem) or xylene (99.99% pure, Sigma Aldrich) to obtain a concentration of 0.15 M . The volumetric flow rate of the precursor at 5 ml / min was defined as the default parameter during synthesis. The solution was atomized at a flow rate of 5 l / min of oxygen and at a nozzle pressure of 1.6 bar using a nozzle. Combustion of the precursor dispersion was introduced with a circulating methane / oxygen flame (1.5 l / min / 3.2 l / min).
The composition of the synthesized phase can be seen from Table 2. Depending on the proportion of precursor used, the composition of the sensitive layer can be systematically obtained. The table shows that the pure In 4 Sn 3 O 12 - phase is present at a tin concentration of 43%.
The sensor substrate (taken out) was placed at a distance of 25 cm above the flame and their backside was cooled with water by means of a corresponding sample holder. The deposition time was 20 minutes.
Table 2: Measured values of expected tin concentration and composition of the obtained material.
(XRD)
(XRD)
Resistance measurement and temperature compensation
The substrate is heated in an oven and the resistance of the heating coil on the backside is measured. The generated calibration curve is used as a reference for operating the sensor.
The sensor is placed in a corresponding measuring chamber connected to a special gas mixing device (Roeck et al. (30)) which has been specially developed for working with small concentrations of formaldehyde. The resistance of the sensitive layer is read by a multimeter (Agilent 34970A), which ensures the collection of data measured in combination with the computer. Figure 2 shows the curve of the resistance measurements as a function of time. To obtain approximate information about the quality of the sensor for a particular application, the data can be converted into sensor signals and sensitivity units by mathematical association. In Fig. 1 , the sensor signals of the sensitive layers of different compositions are displayed. In the composition has a ratio of 43% Sn, the data may be taken directly from the curve of the sensor signal shown in Fig.
Claims (10)
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102010027070A DE102010027070A1 (en) | 2010-07-13 | 2010-07-13 | Gas sensor and method for its production |
| DE102010027070.9 | 2010-07-13 | ||
| PCT/DE2011/001417 WO2012006994A2 (en) | 2010-07-13 | 2011-07-07 | Gas sensor and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
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| KR20130143538A KR20130143538A (en) | 2013-12-31 |
| KR101787153B1 true KR101787153B1 (en) | 2017-11-15 |
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| Application Number | Title | Priority Date | Filing Date |
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| KR1020137000869A KR101787153B1 (en) | 2010-07-13 | 2011-07-07 | Gas sensor and method for producing the same |
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| Country | Link |
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| US (1) | US9091669B2 (en) |
| EP (1) | EP2593779B1 (en) |
| JP (1) | JP5926726B2 (en) |
| KR (1) | KR101787153B1 (en) |
| CN (1) | CN103221809B (en) |
| DE (1) | DE102010027070A1 (en) |
| WO (1) | WO2012006994A2 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| DE102010027070A1 (en) * | 2010-07-13 | 2012-01-19 | Eberhard-Karls-Universität Tübingen | Gas sensor and method for its production |
| CN103439380B (en) * | 2013-09-04 | 2015-01-28 | 浙江工商大学 | Gas detection system for detecting trace benzene |
| CN104181219B (en) * | 2014-08-29 | 2016-08-31 | 武汉理工大学 | A kind of formaldehyde gas sensor |
| DE102015007474A1 (en) | 2015-06-10 | 2016-12-15 | Mtu Friedrichshafen Gmbh | Arrangement with an internal combustion engine |
| CN105628740B (en) * | 2015-12-26 | 2018-11-13 | 周庆芬 | Import and export the online test method of toxic gas formaldehyde in automatic foot-mat |
| CN109324092B (en) * | 2018-08-27 | 2021-07-16 | 天津理工大学 | Mesoporous polycrystalline ZnO nanosheet and preparation method and application thereof |
| RU2723161C1 (en) * | 2019-04-26 | 2020-06-09 | Федеральное государственное бюджетное образовательное учреждение высшего образования "Московский государственный университет имени М.В. Ломоносова" (МГУ) | Gas-sensitive layer for determining formaldehyde in air, sensor with gas-sensitive layer and detector for determining formaldehyde |
| RU193254U1 (en) * | 2019-05-22 | 2019-10-21 | Федеральное государственное бюджетное образовательное учреждение высшего образования "Московский государственный университет имени М.В. Ломоносова" (МГУ) | DETECTOR FOR DETERMINING FORMALDEHYDE IN AIR |
| CN111547772B (en) * | 2020-05-14 | 2022-06-07 | 重庆工商大学 | Zinc tungstate and zinc stannate composite gas sensing material, preparation method and application |
| CN113189089B (en) * | 2021-03-19 | 2022-05-17 | 四川轻化工大学 | Ozone detection reagent and preparation device and preparation method thereof |
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2010
- 2010-07-13 DE DE102010027070A patent/DE102010027070A1/en not_active Withdrawn
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2011
- 2011-07-07 CN CN201180034515.8A patent/CN103221809B/en active Active
- 2011-07-07 WO PCT/DE2011/001417 patent/WO2012006994A2/en active Application Filing
- 2011-07-07 JP JP2013518951A patent/JP5926726B2/en active Active
- 2011-07-07 KR KR1020137000869A patent/KR101787153B1/en active IP Right Grant
- 2011-07-07 US US13/809,631 patent/US9091669B2/en active Active
- 2011-07-07 EP EP11782363.3A patent/EP2593779B1/en active Active
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Also Published As
| Publication number | Publication date |
|---|---|
| KR20130143538A (en) | 2013-12-31 |
| US9091669B2 (en) | 2015-07-28 |
| CN103221809A (en) | 2013-07-24 |
| EP2593779B1 (en) | 2014-05-21 |
| CN103221809B (en) | 2015-09-23 |
| DE102010027070A1 (en) | 2012-01-19 |
| WO2012006994A2 (en) | 2012-01-19 |
| JP2013531250A (en) | 2013-08-01 |
| EP2593779A2 (en) | 2013-05-22 |
| WO2012006994A3 (en) | 2012-04-12 |
| US20130111974A1 (en) | 2013-05-09 |
| JP5926726B2 (en) | 2016-05-25 |
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